Advanced thermoelectric applications for high efficiency thermoelectric materials include solid state thermoelectric devices for converting thermal energy into electrical energy and for cooling using electricity. Thermoelectric technology is of interest in the automotive industry due to the potential for waste heat recovery to improve fuel economy and for environmentally-friendly cooling. Because the performance of a thermoelectric device depends pivotally on its material properties, much effort has been expended to develop improved thermoelectric materials.
The thermoelectric efficiency of a material is expressed by the dimensionless figure of merit, ZT=S2T/ρκ, where T is the absolute temperature; S is the Seebeck coefficient (thermopower); ρ is the electrical resistivity; and κ is the thermal conductivity. The Seebeck coefficient (S) is a measure of how readily the respective charge carriers (electrons or holes) can transfer energy as they migrate through a thermoelectric material which is subjected to a temperature gradient. The type of charge carriers, whether electron or hole, depends on the dopants (N-type or P-type) in the semiconductor materials used to form the thermoelectric material.
The thermoelectric figure of merit (ZT) is related to the strength of interactions between the charge carriers and the vibrational modes of the crystal lattice structure (phonons), as well as the available energy states of the charge carriers. Both the crystal lattice structure and the energy states of the charge carriers depend on the materials selected to form the thermoelectric device. As a result, the thermal conductivity (κ) is a function of both an electronic component (κe), which is primarily associated with the respective charge carriers, and a lattice component (κL), which is primarily associated with the propagation of phonons through the crystal lattice structure.
In an effort to increase ZT, many material exploration and optimization investigations have been undertaken to lower the lattice thermal conductivity (κL) without deteriorating the power factor (S2/ρ). For example, in thermoelectric materials such as skutterudites, clathrates and chalcogenides, all of which have a microscopic cage-like matrix structure, guest ions interstitially inserted into the voids of the crystal lattice of the materials exhibit large atomic displacement parameters. These guest ions, termed “rattlers”, interact with low-frequency lattice phonons. This interaction significantly reduces κL, leading to substantial ZT increases at both low and high temperatures. Other methods of enhancing ZT have included the introduction of simultaneous isoelectronic alloying and doping on different crystallographic sites (in the case of half-Heusler structures), as well as the introduction of point defects in the lattice structure to increase phonon scattering.